Organoboron‐Functionalized Metal‐Organic Nanosheets for Highly Efficient CO₂ Fixation Mediated by Frustrated Lewis Pairs

Abstract

Abstract Converting CO 2 to high‐value fine chemicals represents one of the most promising approaches to combat global warming and subsequently achieve a sustainable carbon cycle. Herein, we contribute an organoboron functionalized ultra‐thin metal‐organic nanosheet (MON), termed TCPB‐Zr‐NS, featuring an abundance of exposed Lewis acidic B and formate sites, which can effectively promote CO 2 conversion upon the addition of Lewis basic o‐phenylenediamines. Compared with the prototypical 3D analogue TCPB‐Zr‐3D, the resultant TCPB‐Zr‐NS showcases dramatically improved catalytic activity for the cyclization of o‐phenylenediamine as a result of the highly exposed active sites and efficient substrates/products diffusion. Strikingly, the incorporation of Lewis acidic B sites into ultra‐thin Zr‐based MON (Zr‐MON) not only promotes the highly efficient CO 2 conversion, but also enhances the recyclability/durability of catalysts. Additionally, the underlying catalytic mechanism has been well established by the comprehensive experiments and theoretical calculations, unveiling a formate‐assisted frustrated Lewis pairs (FLP) mediated catalytic pathway. This work opens up a new avenue to heterogeneous FLP‐based catalysts for small molecule activation and beyond.